Process for the dyeing of stereoregular polypropylene textile materials with aqueousdispersions containing waterinsoluble dyestuffs



United States Patent Britain N0 Drawing. Filed Feb. 27, 1963, Ser. No. 261,516 Claims priority, application G/reat Britain, Feb. 28, 1962, 62

2 Claims. (Cl. 855) This invention relates to a dyeing process for textile materials comprising polyolefine fibres especially fibres of stereoregular polypropylene.

Polyolefine fibres, being composed entirely of carbon and hydrogen, are not dyed satisfactorily from aqueous dyebaths by means of dyes which are commonly used for other fibres. The dyestufis which have hitherto been considered to have the best affinity for polyolefine fibres are those in which a portion of the molecule is of aliphatic or cycloaliphatic character. All dyestuffs which have hitherto been employed for dyeing polyolefine fibres, however, fail to build up satisfactorily, so that dyeings of deep shade cannot be obtained. Furthermore those dyes which are known to build up even moderately well are easily removed from the fibre by treatment with drycleaning solvents such as perchloroethylene.

It has been proposed to mass-colour polyolefines before spinning into fibre, but even this process is at present unsatisfactory because many dyes have only low degrees of compatibility with the polymer so that homogeneous deep shades cannot be obtained.

It has been also proposed to manufacture polyolefine fibres which contain metallic compounds such as zinc and magnesium stearates, so that dyeing, particularly in deep shades may be accomplished from aqueous dyebaths by means of dyestuffs which react with the metal.

Other proposals have been made for modifying polyolefine textile material in order to make it more easily dyeable by including additives which have afiinity for the dyestuffs and by various forms of chemical treatment.

We have now found that water-insoluble dyestuffs containing at least one fully substituted amide group (that is to say, an amide group in which the nitrogen atom is not attached to a hydrogen atom) have good afiinity for polyolefine textile materials, including ordinary unmodified stereoregular polypropylene, and may be applied in simple manner to give dyeings of deep shade s and good fastness properties.

uAccording to the invention therefore we provide a process for the dyeing of polyolefine textile materials which comprises applying to said textile'material a waterinsoluble dyestufif containing at least one fully substituted amide group.

The water-insoluble dyestuffs used in the process of the inven i n may he of any desired series, but preferably th y are llie monoazo, disazo, anthraquinone, methine, a lhe or nitrodiphenylamine series, dyestufis f ltihoazo and disazo series being of special interest. They may, however, be of other series, for exampethe quinphthalone, oxazine, dioxazine, azine, tlnazine, triphenyl methane, tetrazaporphin, or diphenylmethane series.'

The dyestuffs, being water-insoluble are devoid of sulphonic and carboxylic acid groups and quaternary ammonium salt groups. In the water-insoluble dyestuffs, the colour-providing (chromophoric) portion of the dye stufi molecule may be attached either to the nitrogen 3,171,710 Patented Mar. ,2, 1965 atom of the amide group or it may be attached to or form part of the acyl radical of the amide group.

More particularly the water-insoluble dyestuffs used in the process of the invention may be of the formula wherein D represents the colour-providing portion of the dyestufi molecule, R represents a lower alkyl or substituted alkyl, cycloalkyl, aralkyl or aryl radical, n is preferably 1, but may be 2 or 3 and X is joined to a cyclic or non-cyclic carbon atom of D and represents a group of the formula GOZlI, SOZII\T, r 0o, l Is0z, or -N- in which Z represents the atoms necessary to complete a diazine or triazine ring which may carry other substituents, R represents a lower alkyl, substituted alkyl, cycloalkyl or aralkyl radical, or in the cases when X represents a radical of the formula then R and R may together represent the atoms necessary to form with the amide nitrogen atom a heterocyclic ring which may contain other hetero atoms.

Preferably the (X-R) group contains not more than 8 carbon atoms.

In the foregoing paragraph the term lower alkyl radical may be exemplified by methyl, ethyl, n-propyl, n-butyl, isopropyl and tert-butyl; substituted lower alkyl radical may be exemplified by diethylaminoethyl, dipropylaminoethyl, diethylaminomethyl, chloromethyl, ethylthiomethyl, cyclohexylmethyl, fi-acetoxyethyl and {S-methoxyethyl; cycloallcyl radical may be exemplified by cyclohexyl; aralkyl radical may be exemplified by benzyl and fl-phenylethyl; and aryl radical may be exemplified by phenyl, p-tolyl, p-chlorophenyl and w and S-naphthyl.

As examples of diazine and triazine rings which may be completed by Z we mention 1:3-diazine and 1:3:5-triazine rings and especially such rings carrying substituents such as chlorine atoms, amino, alkylamino (e.g., methylamino), dialkylamino (e.g., diethylamino) or alkoxy (e.g., methoxy) groups.

As examples of heterocyclic rings which may together be represented by R, R and the amide nitrogen atom, when X represents we mention piperidine, morpholine and piperazine.

Specifically, we mention the following as examples of fully substituted amide groups of the formula -X-R which may be present in the dyestuiis used in the process of our invention:

. d -nu y mi lp onyl,

di-n-prop-ylaminosulphonyl, N-methyl-N-cyclo-hexylaminosulphonyl, N-methyleNephenylaminosulphonyl, N-piperidylsulp-honyl,

N (N -methylpiperazylsulphonyl, N-methyl-N-acetylamino,

N-ethyl-N-acetylamino,

Of especial interest in the process of the invention are those dystuifs of the aforesaid formula wherein (l) X represents and R and R represents alkyl radicals. (2 X represents RI 1 1o0- and R represents an alkyl radicaL I Such dyes have quite exceptional building-up properties on unmodified polypropylene textile materials, giving very deep shades of high fastness properties.

treated in a solution of soap or synthetic detergent and dried.

It is known to dye textile materials comprising poly olefine fibres with certain water-insoluble dyestuffs of the azo series containing amide groups. In all the amidecontaining dyestuffs hitherto used for this purpose the nitrogen atom of the amide group is attached to at least one hydrogen atom. Compared with such dyestuffs, the dyestuifs. used in the process of our invention have greater affinity and superior build-up properties on stereoregular polypropylene fibres and the dyeings obtained are of much better fastness to the action of solvents such as perchloroethylene which are used in dry cleaning.

The invention is illustrated but not limited by the following examples in which the parts are by weight.

Example 1 1 part of the dyestuif obtained by coupling diazotised 4-(N:N-dimethylaminocarbonyl) aniline with p-(t-butyl)- phenol is milled with 20 parts of water and 1 part of a sulphonated naphthaleneformaldehyde condensation product and the dispersion so obtained is added to 4000 parts of Water containing 4 parts of the sulphonated naphthalene formaldehyde condensate. 100 parts of polypropylene textile material is immersed in the dyebath so obtained and the temperature is raised to 100 C. Dyeing is carried out for 90 minutes at this temperature. The dyed fibre is then treated for 15 minutes in a warm aqueous'solution of a synthetic detergent. The polypropylene fibre is dyed a bright reddish yellow shade of very good fastness to light, to Washing and to dry cleaning with solvents such as perchloroethylene.

In place of the sulphonated naphthalene-formaldehyde I 1 condensation. product used asdispersing agent there may The dyestuifs used in the process of our invention may 1' be obtained by methods known in the art for the production o-famides, for example by interacting appropriate amines and acid chlorides; Alternatively the dyestuffs may be obtained from dyestuffintermediates containing fully substituted amide groups. For example azo dyestuifs suitable. for use in the process of our invention may be obtainedby the use of diazo and/or coupling components which contain fully substituted amidegroups.

The water-insoluble dyestuff containing fully substituted amide groups may be applied to the prolyolefine textile.

material from a solution inv an organic solvent, but it is preferred to apply the water-insoluble dyestuff from a dye liquor comp-rising an aqueous dispersion of the dyestuff.

In the preparation of such dye liquors it is advantageous to employ dispersing agents, which maybe of the anionic type, for example sulphonated naphthalene-formaldehyde condensation products, the cationic type, for example cetyltrime'thylammonium bromide, or the non-ionic type,

for example the condensation product of ethylene oxide with a fatty alcohol. In some cases, notably where the dyes contain dialkyl amino groups cleaner and brighter dyeings may be produced by dyeing from a dyebath which contains a non-ionic dispersing agent andwhich'may be alkaline. V

The process of the invention is preferably carried out by immersing the polyolefine textile material in a dyebath comprising an aqueous dispersion of the dyestuff and a heating the dyebath to between and C. at atmospheric pressure, or to between 100" C. and 12 5f C. under super-atmospheric pressure. Dyeing is usually complete in about 15 minutes to 1 hour and the textile material may then be removed from the dyebath, rinsed,

be used other anionic dispersing agents, or cetyltrimethylammonium bromide or other cationic dispersing agents.

The best results are obtained by using non-ionic dispersing agents of which the condensate of ethylene oxide (e.g., 17 moles) with cetyl alcohol is exemplificatory. When a non-ionic dispersing agent is used, the dyebath may, if desired'be made alkaline.

When the dyestuff in Example 1 is replaced by the dyestuffslisted in column 2 of the following table, dyeings of the shade in column 3 are obtained. These dyestuffs all have good building-up properties and good fastness to washing and to dry cleaning with solvents such as perchloroethylene.

. Shade on Example Dyestufi polypropylene -2 2-l1ydroxy-4-dimethylaminocarbonyl-5-mothyl- Yellow.

azobenzene. 3 2-hydroxy-2-dimethylaminocarbonyl-5-tert. Do.

butylazobenzene. 4 2'hydr0xy-4-diethylaminocarbonyl-5-tert.butyl- Do. azobenzene. 5. 2-liydroxy-4'-diethylamiuocarbonyl-5-methylazo- 00.

benzene. 6 2-hydroxy-4-dimethylaminocarbonyl-S-cyclo- D0.

hexylazobenzene. 7 2-hydr0xy-4-di-n-propylarninocarbonyl-5- D0.

methylaaobenzene. 8; 2-hydroxy-4'-di-n-propylarninocarbonyl D0.

. butylazaobenzene. a 9 2-hydroxy-4-diisopropylaminocarb n Do. methylazobenzenc. 1O 2-hydroxy-4-diisopropylamin0carbdQ ert. D0.

butylazobenzene. 11 ,2-hydroxy-4-(N-methyl-N-B-diethylarnlllfi y Do.

, aminocarbonyl-5methylazobenzene. a, 12 2-hydroxy-4-(4"-rnethylpiperazinyloarbonylfi- D0. methylazobenzene, 13 2-(4-dimethylaminocarbonylphenylazo)-4- REE'Z methyl-l-naphthol. a 14 2-(4-diethylaminoearbonylphenylazo)-4- Do. methyl-l-naphthol. 15 2-(3-dimethylaminocarbonylphenylazo)-4- D0.

' methyl-l-naphthol. 16 2-(4-diethylaminocarbonylphenylazo)-4-n-butyl- Do.

l-naplithol. 17 4diethylamino-4-diethylaminocarbonylfl- Orange.

methylazobenzene. 1 8 4-diethylan1ino-4-dimethylaminooarbony1-2- D0.

methylazobenzene.

7 *tile material a dye'liquor consisting'of an aqueous disper- 2,112,403 sion of a water-insoluble dyestuif containing at least one 2,633,461 fully substituted amide group. 7 7

References (Zited'by'the Examiner 5 809,495 UNITED STATES PATENTS 814,582

1,995,933 3/35 Laska et' a1. 260-204X 8 3/38 Krzikalla et-al. 260204 3/53 7 Seidenfaden et a1. 260- 207 FOREIGN PATENTS 2/59 Great Britain. 6/59 Great Britain.

NORMAN G. TORCHIN, Primaly Ekaminer. 

1. PROCESS FOR THE DYEING OF STEREOREGULAR POLYPROPYLENE TEXTILE MATERIALS WHICH COMPRISES APPLYING TO SAID TEXTILE MATERIAL AN AQUEOUS DISPERSION OF A WATER-INSOLUBLE DYESTUFF OF THE FORMULA 